TWI663240B - Adhesive film - Google Patents

Abstract

The adhesive film disclosed by the present invention has (α) a poly (meth) acrylimide resin film layer and (γ) an adhesive layer in order from the surface layer side, and the total light transmittance is 80%. The adhesive film may further have a (δ) hardened coating layer on the surface side of the (α) poly (meth) acrylimide resin film layer. The (δ) hardened coating layer may include: (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) one having an alkoxysilyl and (meth) acryloyl groups; 0.2 to 4 parts by mass of the compound; (C) 0.05 to 3 parts by mass of organic titanium; and (D) an active energy ray-curable resin composition of 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm. The active energy ray-curable resin composition may further include (E) water repellents at 0.01 to 7 parts by mass.

Description

Adhesive film

The present invention relates to an adhesive film. The present invention relates in more detail to an adhesive film having excellent transparency, color tone and surface appearance, and at the same time preferably abrasion resistance, surface hardness and bending resistance.

In recent years, it is popular to install a touch panel on an image display device such as a liquid crystal display, a plasma display, or an electroluminescence display, and touch the panel with a finger or a pen to input while looking at the display. The display panels of image display devices (including image display devices with touch panel functions and image display devices without touch panel functions) are required to have heat resistance, dimensional stability, high transparency, high surface hardness and Due to its high rigidity and other characteristics, glass-based articles have been used. In addition, glass has defects such as low impact resistance and easy breakage. Therefore, it has been disclosed that various films are attached on the surface of the display panel for the purpose of preventing glass breakage (for example, refer to Patent Documents 1 and 2). However, the wear resistance of these films is not very satisfactory.

In addition, glass also has low workability, is not easy to handle and handle, the specific gravity is heavy, and it is not easy to respond to the display of curved surface or the requirements of flexibility and other missing issues. So some people will Extensive research to replace glass materials. Multiple disclosures are due to the transparency of triacetylcellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymers On the surface of the resin film substrate, a cured coating layered body having a cured coating with excellent surface hardness and abrasion resistance is formed (for example, refer to Patent Document 3). However, the wear resistance of such a hardened coating is not very satisfactory.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP 2008-095064

[Patent Document 2] JP 2010-275385

[Patent Document 3] JP 2013-208896

The object of the present invention is to provide an adhesive film which is excellent in transparency, color tone and surface appearance, and at the same time preferably has abrasion resistance, surface hardness and bending resistance.

As a result of careful research, the present inventors have found that the above-mentioned problems can be achieved by using a poly (meth) acrylimide resin film layer as a film substrate.

That is, various aspects of the present invention are as follows.

[1] An adhesive film comprising (α) a poly (meth) acrylimide resin film layer and (γ) an adhesive layer in this order from the surface layer side, and the total light transmittance is 80%.

[2] The adhesive film according to the above item [1], further comprising a (δ) hardened coating layer on a surface side of the (α) poly (meth) acrylimide resin film layer.

[3] The adhesive film according to the above item [2], wherein the (δ) hardened coating layer is composed of: (A) a polyfunctional (meth) acrylate in 100 parts by mass; (B) an alkane Compounds of alkoxysilyl and (meth) acryloyl 0.2 to 4 parts by mass; (C) Organic titanium 0.05 to 3 parts by mass; and (D) 5 to 100 particles having an average particle diameter of 1 to 300 nm It consists of an active energy ray-curable resin composition in the mass part.

[4]. The adhesive film according to the above item [3], wherein the active energy ray-curable resin composition further contains (E) water repellents at 0.01 to 7 parts by mass.

[5]. The adhesive film according to the above item [4], wherein the (E) water repellent is a fluoropolyether water repellent containing a (meth) acryloyl group.

[6]. The adhesive film according to any one of the above [1] to [5], wherein the (α) poly (meth) acrylimide resin film layer satisfies the following characteristics (I) and (II) ) (I) The total light transmittance is 85% or more; (II) The haze value is 3.0% or less.

[7]. The adhesive film according to any one of the above [1] to [5], wherein the (α) poly (meth) acrylimide resin film layer is directly and sequentially laminated: the first polymer (Meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); and a second poly (meth) acrylimide resin layer (α2).

[8]. The adhesive film according to any one of the above [1] to [7], wherein the (γ) adhesive layer contains a silicon adhesive.

[9]. An adhesive film for use as a component of an image display device according to any one of [1] to [8] above.

[10]. An image display device member comprising the adhesive film according to any one of the above [1] to [8].

The adhesive film of the present invention has not only transparency, good hue and surface appearance, but also preferably abrasion resistance, and good surface hardness and bending resistance. In addition, the adhesive film of the present invention is excellent in appearance protection and adhesiveness when it does not allow air bubbles to be sucked in and peels off. Therefore, the adhesive film can be used as a display panel or is preferably used as a protective film for a display panel.

1‧‧‧Squeezer 1

2‧‧‧Squeezer 2

3‧‧‧2 types of 3 layers multi-manifold method for common extrusion T-die

4‧‧‧ melting film

5‧‧‧Mirror Roller

6‧‧‧Mirror Conveyor Belt

7‧‧‧ Pair of Conveyor Rollers

FIG. 1 is a schematic view showing a film forming apparatus used in Example 1 for a transparent multilayer film (α-1).

The adhesive film of the present invention includes, in order from the surface layer side, a (α) poly (meth) acrylimide resin film layer and a (γ) adhesive layer. The so-called "surface layer side" here means that the article formed by the adhesive film of the coating structure is closer to the outer surface (display panel or Visible surface when protecting film). In addition, in this specification, the "surface side" of arranging a certain layer on another layer includes directly connecting these layers and interposing other singular or plural layers between these layers.

(α) Poly (meth) acrylimide resin film layer

The (α) poly (meth) acrylimide resin film layer is a layer formed of a poly (meth) acrylimide resin film. By using the poly (meth) acrylimide resin film layer, the transparency, hue, abrasion resistance, surface hardness, bending resistance, and surface appearance of the adhesive film of the present invention are made good.

The aforementioned poly (meth) acrylimide resin has the characteristics of so-called acrylic resin, such as high transparency, high surface hardness and high rigidity, and can be directly introduced into the characteristics of polyimide resin with good heat resistance or dimensional stability, which has been improved. Thermoplastic resin that has the disadvantages of coloring from light yellow to reddish brown. The poly (meth) acrylamide imide resin is disclosed, for example, in Japanese Patent Publication No. 2011-519999. In addition, in the present specification, the term "poly (meth) acrylamide" means "polyacrylamide" or "polymethacrylimide".

For the purpose of using an adhesive film for optical articles such as touch panels, there is no restriction except that it has high transparency and no coloring. Any poly (meth) acrylimide resin can be used. As the poly (meth) acrylimide resin.

Examples of the preferable poly (meth) acrylic acid imide resin include a yellowness index (based on JIS K7105: 1981 and using a colorimeter "SolidSpec-3700" manufactured by Shimadzu Corporation). (Trade name) measured) is 3 or less. The yellowness index of the poly (meth) acrylimide resin is preferably 2 or less, and most preferably 1 or less. In addition, from the standpoint of the compression load or the stability of the melted film, as a preferred poly (meth) acrylic acid imide resin, a melt volume-flow rate (MFR) basis can be cited. ISO1133 and measured at 260 ° C and 260 ° C under 98.07N) are 0.1 to 20 g / 10 minutes. The melt mass flow rate of the poly (meth) acrylimide resin is preferably 0.5 to 10 g / 10 minutes. In addition, from the viewpoint of heat resistance, the glass transition temperature of the poly (meth) acrylamide imide resin is preferably 150 ° C or higher. It is more preferable if the glass transition temperature is 170 ° C or higher.

In addition, in the above poly (meth) acrylic fluorene imine resin, as long as it does not violate the purpose of the present invention, it may further include: a thermoplastic resin other than the poly (meth) acrylic fluorene imine resin; a pigment , Inorganic filler (filler), organic filler, resin filler; lubricants, antioxidants, weather-resistant stabilizers, heat stabilizers, parting agents, antistatic agents and surfactants (surfactant) and other additives. In general, when the poly (meth) acrylamide imide resin is 100 parts by mass, the blending amount of these optional components is about 0.01 to 10 parts by mass.

Examples of poly (meth) acrylamidoimide resins currently on the market include "PLEXIMID TT50" (trade name) and "PLEXIMID TT70" (trade name) "by Japan's EVONIK.

The above poly (meth) acrylimide resin film is preferably directly laminated sequentially: the first poly (meth) acrylimide resin layer (α1); the aromatic polycarbonate resin layer (β); And a transparent multilayer film of a second poly (meth) acrylimide resin layer (α2). In addition, in the present specification, the present invention is described by arranging the α1 layer on the surface layer side.

Poly (meth) acrylic acid imide resin is thin, although its surface hardness is better, it does not have high punchability. In contrast, although aromatic polycarbonate resins have good punching resistance, they do not have high surface hardness. Therefore, by forming the above-mentioned layer structure and combining the advantages of both, a transparent multilayer film having excellent surface hardness and punching resistance can be obtained.

Although there is no particular limitation on the layer thickness of the α1 layer, from the viewpoint of heat resistance or surface hardness of the adhesive film of the present invention, it is usually 10 μm or more, preferably 20 μm or more, more preferably 40 μm or more, and most preferably 60 μm. the above.

Although the layer thickness of the α2 layer is not particularly limited, from the viewpoint of curl resistance of the adhesive film of the present invention, it is preferable that the layer thickness be the same as the α1 layer.

In addition, the so-called "same layer thickness" herein should not be interpreted in the strict sense of physical chemistry. It should be interpreted to be the same layer thickness within the range of quality control change steps usually performed in the industry. If the same layer thickness is used within the range of the steps and quality control changes usually performed in the industry, the curl resistance of the multilayer film can be well maintained. In the case of a non-stretched multilayer film formed by a co-extrusion method of a T-die, the steps and quality control are usually performed with a varying width of about -5 to +5 μm, so it should be interpreted as a layer thickness of 65 μm The same as the same 75 μm. The "same layer thickness" herein may also be referred to as "substantially the same layer thickness".

The layer thickness of the β layer is not particularly limited, but from the viewpoint of cutting resistance of the adhesive film of the present invention From a viewpoint, it is usually 20 μm or more, preferably 40 μm or more, and most preferably 60 μm or more.

The poly (meth) acrylimide resin used for the α1 layer and the α2 layer is as described above.

In addition, the poly (meth) acrylic acid imide resin used for the α1 layer and the poly (meth) acrylic acid imine resin used for the α2 layer have different resin characteristics, such as the melt quality. Poly (meth) acrylamide imine resins with different melt volume-flowrate (MFR) or glass transition temperature. However, from the viewpoint of curl resistance of the transparent multilayer film, it is preferable to use the same resin characteristics. For example, it is possible to use the same block of the same level as one of the preferred embodiments.

As the aromatic polycarbonate resin used for the β layer, for example, bisphenol A, dimethylbisphenol A, and 1,1-bis (4-hydroxyphenyl) -3,3,5- Polymers obtained by interfacial polymerization of aromatic dihydroxy compounds such as trimethylcyclohexane and phosgene; bisphenol A, dimethylbisphenol A, and 1,1-bis (4-hydroxyphenyl) One or two types of aromatic polycarbonates such as polymers obtained by transesterification of an aromatic dihydroxy compound such as -3,3,5-trimethylcyclohexane and dicarbonate such as diphenyl carbonate More than one kind of mixture.

As a preferable arbitrary component which can be contained in the said aromatic polycarbonate, a core-shell rubber is mentioned, for example. When the sum of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass, it is preferable to use 0 to 30 parts by mass of the core-shell rubber (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably The amount is 0 to 10 parts by mass (100 to 90 parts by mass of the aromatic polycarbonate resin) to further improve cutting workability or impact resistance.

Examples include: methacrylate styrene / butadiene rubber graft copolymer, acrylonitrile styrene / butadiene rubber graft copolymer, acrylonitrile styrene / ethylene propylene rubber graft copolymerization Core-shell rubbers such as acrylics, acrylonitrile, styrene / acrylate graft copolymer, methacrylate / acrylate rubber graft copolymer, methacrylate, acrylonitrile / acrylate rubber graft copolymer, etc. Core-shell rubber. As the core-shell rubber, one or more of these core-shell rubber mixtures can be used.

In addition, the above-mentioned aromatic polycarbonate resin may further include: a thermoplastic resin other than the aromatic polycarbonate resin or the core-shell rubber; a pigment, an inorganic filler, and an organic filler, as long as the principle of the present invention is not violated. , Resin fillers; lubricants, antioxidants, weather-resistant stabilizers, thermal stabilizers, parting agents, antistatic agents and surfactants and other additives. In general, when the total amount of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass, the blending amount of these optional components is about 0.01 to 10 parts by mass.

The manufacturing method for obtaining the poly (meth) acrylamidoimide resin film is not particularly limited, but examples include: (A) the use of a device equipped with an extruder and a T-die, from the T-die The step of continuously extruding the melted film of poly (meth) acrylic acid imide resin; (B) between the first mirror body that rotates or circulates and the second mirror body that rotates or circulates, the above poly (methyl) ) A method of melting a thin film of acrylimide resin and performing a pressing step.

Similarly, although there is no special limitation, the above-mentioned α1 layer, β layer, and α2 layer are directly laminated in this order. The method for producing a transparent multilayer film of poly (meth) acrylic acid imide resin film is described, but it includes: (A ') the use of a co-extrusion device equipped with an extruder and a T-die, and T-die continuous co-extruding according to the first poly (meth) acrylic acid imide resin layer (α1); aromatic polycarbonate resin layer (β); the second poly (meth) acrylic acid imide resin layer (α2) the step of melting the transparent multilayer film directly laminated in this order; (B ') between the rotating or circulating first mirror body and the rotating or circulating second mirror body, supplying the transparent multilayer film A method of melting a film and performing a pressing step.

Any conventional technique can be used as the above-mentioned T-die for the above-mentioned step (A) or the above-mentioned step (A '). For example, any known molds such as a manifold mold (manifold tie), a fishtail tie, and a coat hanger tie can be mentioned.

Any conventional technique can be used as the above-mentioned co-extrusion device. For example, a common pressing device such as a feed block method, a multi-manifold method, and a stacked plate method can be cited.

Any conventional technique can be used as the above-mentioned press for the above-mentioned step (A) or the above-mentioned step (A '). For example, a uniaxial press, a biaxial press that rotates in the same direction, and a biaxial press that rotates in different directions can be mentioned.

In addition, in order to suppress the deterioration of the poly (meth) acrylic imide resin or the aromatic polycarbonate resin, a nitrogen purge is preferably provided in the extruder.

In addition, poly (meth) acrylic imide resin is a resin with high hygroscopicity, so it is preferable to dry it before forming a film. In addition, it is preferred that the poly (meth) acrylic imide resin dried by the dryer is directly conveyed from the dryer and then put in. The temperature setting of the dryer is preferably 100 to 150 ° C. In addition, it is preferable to provide a vacuum vent in the extruder (usually, in the metering area at the front end of the screw).

For the temperature of the T-shaped mold used in the step (A) or the step (A '), in order to make the molten film of the poly (meth) acrylic imide resin or the molten film of the transparent multilayer film stable and continuous In the pressing or co-extrusion step, the temperature is preferably set to at least 260 ° C or more, and more preferably 270 ° C or more. In order to suppress the deterioration of the poly (meth) acrylic imide resin or the aromatic polycarbonate resin, the temperature of the T-die is preferably set to 350 ° C or lower.

In addition, the lip opening (R) and the thickness (T) ratio (R / T) of the obtained poly (meth) acrylic imide resin film are from the viewpoint of not increasing the optical retardation. In view of this, it is usually 10 or less, and preferably 2.5 or less. In addition, from the viewpoint of not excessively pressing the load, (R / T) is preferably 1 or more, and more preferably 1.5 or more.

Examples of the first mirror surface used in the step (B) or the step (B ') include a mirror roller or a mirror conveyor. Examples of the second mirror body include a mirror roller and a mirror conveyor.

The surface of the mirror roller is a mirror-finished roller. Mirror rollers are made of metal, ceramic and silicone. In addition, on the surface of the mirror roller, in order to protect against corrosion or scratches, For the purpose, chromium plating or iron-phosphorus plating alloys can be performed, and hard carbon can be processed by PVD method or CVD method.

The surface of the above-mentioned mirror conveyor belt is mirror-finished, and it is usually a metal seamless belt. For example, a pair of belt rollers can be wound around each other and can be circulated. In addition, the surface of the mirror conveyor belt can be chrome-plated or iron-phosphorus-plated alloy for the purpose of protecting against corrosion or scratches, and hard carbon can be treated by PVD method or CVD method.

The mirror processing is not particularly limited, and can be performed by any method. For example, the method can be: grinding the fine particles to make the arithmetic average roughness (Ra) of the surface of the specular body 100 nm or less, and 50 nm or less is the best, and the ten-point average roughness (Rz) It is preferably 500 nm or less, and most preferably 250 nm or less.

Although it is not intended to be logically restricted, the poly (meth) acrylamidoimide resin film or transparent multilayer film with excellent transparency, surface smoothness, and appearance obtained by the above-mentioned film forming method can be considered for use in the first On the specular body and the second specular body, the height of the first specular body and the second specular body is made smooth by extruding the melted film of the poly (meth) acrylamide resin film or the transparent multilayer film. The state is transferred to the film to correct defects such as dai-line.

In order to perform the above-mentioned surface state transfer, the surface temperature of the first mirror body is usually 70 ° C, preferably 100 ° C or more, more preferably 120 ° C or more, and most preferably 130 ° C or more. In addition, in order to prevent appearance defects (peel marks) accompanying the peeling from the first mirror body to appear on the film, the surface temperature of the first mirror body is preferably 200 ° C or lower, more preferably 160 ° C or lower.

In order to enable the above-mentioned surface state transfer to be performed well, the surface temperature of the second mirror body is usually 10 ° C or higher, and preferably 20 ° C or higher. Its surface temperature is preferably 60 ° C or higher and more preferably 100 ° C or higher. In addition, in order to prevent appearance defects (peel marks) accompanying the peeling from the second specular body from appearing on the film, the surface temperature of the second specular body is preferably 200 ° C or lower, more preferably 160 ° C or lower.

The surface temperature of the first mirror body is preferably higher than the surface temperature of the second mirror body. This is because the film is coated on the first mirror body and sent out to the next conveying roller.

The thickness of the poly (meth) acrylic imide resin film (including the above-mentioned transparent multilayer film. The same applies hereinafter) is not particularly limited, and it can be made into any thickness as desired. When the adhesive film of the present invention is used as a display panel, the thickness of the poly (meth) acrylic imide resin film is usually 100 μm or more, preferably 200 μm or more, and more preferably 300 μm or more from the viewpoint of maintaining rigidity. . In addition, from the viewpoint of meeting the requirements for thinness of the image display device, the thickness of the poly (meth) acrylic imide resin film is usually 1500 μm or less, preferably 1200 μm or less, and more preferably 1000 μm or less. When the adhesive film of the present invention is used to protect the surface of a display panel, from the viewpoint of operability, the thickness of the poly (meth) acrylic imide resin film is usually 20 μm or more, and more preferably 50 μm or more. In addition, from the viewpoint of economy, the thickness of the poly (meth) acrylic imide resin film is usually 250 μm or less, and preferably 150 μm or less.

The total light transmittance of the aforementioned poly (meth) acrylic imide resin film (measured in accordance with JIS K7361-1: 1997 and using a turbidimeter "NDH2000 (trade name) by Nippon Denshoku Industries Co., Ltd."), compared with It is preferably 85% or more, more preferably 88% or more, followed by 90% or more, and most preferably 92% or more. The higher the total light transmittance of the poly (meth) acrylic imide resin film, the better. By making the poly (meth) acrylic imide resin film have such a high total light transmittance, a better use can be obtained. Adhesive film on the components of the image display device.

The haze value of the above poly (meth) acrylic imide resin film (measured in accordance with JIS K7136: 2000 and using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.), preferably 3.0% or less It is better if it is 3.0% or less, followed by 2.1% or less, followed by 2.0% or less, and 1.5% or less. The lower the haze value of the poly (meth) acrylic imide resin film, the better. By allowing the poly (meth) acrylic imide resin film to have such a low haze value, it is possible to obtain an adhesive film which is preferably used for an image display device member.

The yellowness index of the poly (meth) acrylic imide resin film (measured in accordance with JIS K7105: 1981 and using a colorimeter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation) is preferably 3 or less, more preferably 2 or less, and most preferably 1 or less. The lower the yellowness index of the poly (meth) acrylic imide resin film, the better. By allowing the poly (meth) acrylic imide resin film to have such a low yellowness index, it is possible to obtain an adhesive film which is preferably used for an image display device member.

When the poly (meth) acrylic imide resin film is used to form the (γ) adhesive layer or the (δ) hardened coating layer, in order to improve the bonding strength, a tip discharge treatment may be performed on the at least one sheet in advance. Or it can be easily processed by thickening coating.

When performing the above-mentioned tip discharge treatment, a good indirect adhesion strength can be obtained by letting the wetness index (measured in accordance with JIS K6768: 1999) be generally 50 mN / m or more, preferably 60 mN / m or more. In addition, after the tip discharge treatment is performed, a thickened coating can be formed.

Tip discharge treatment is to treat the surface of the film by passing the thin film between the insulated electrode and the dielectric roller and applying high-frequency high voltage to generate a sharp discharge. By this tip discharge, oxygen and the like are ionized, and by hitting the surface of the film, the resin molecular chain is cut off or an oxygen-containing functional group is applied to the resin molecular chain to increase the wetness index.

The unit area of the above-mentioned tip discharge treatment, and the treatment amount (S) per unit time are determined from the viewpoint of obtaining the above-mentioned wetting index. The treatment amount (S) is usually 80W‧min / m ² or more, preferably 120W. ‧Min / m ² or more. In addition, from the viewpoint of preventing deterioration of the thin film, it is preferable that the processing amount (S) be suppressed to 500 W · min / m ² or less. The best processing capacity (S) is 400W‧min / m ² or less.

The processing amount (S) is defined as follows.

S = P / (L‧V) where S: processing capacity (W‧min / m ² ); P: discharge power (W); L: length of discharge electrode; V: linear velocity (m / min).

The tackifier coating agent used to form the above-mentioned tackifier coating is not particularly limited except that it has high transparency and no coloring. For example, conventional techniques such as polyester, acrylic, polyurethane, acrylic polyurethane, and polyester polyurethane can be used as anchor coating agents. agent). Among these, from the viewpoint of improving the bonding strength with the (γ) adhesive layer or the (δ) hardened coating layer, a thermoplastic polyurethane tackifying coating agent is preferred.

In addition, a coating material containing a silane coupling agent may be used as the tackifier coating agent. Silane coupling agents have hydrolyzable groups (such as alkoxy groups such as methoxy and ethoxy groups; acyloxy groups such as acetoxy groups; halogen groups such as chloro groups) and organic functional groups (such as amino and vinyl groups) , Epoxy group, methacryloxy group, acryloyloxy group, isocyanate group, etc.) at least two types of silane compounds having different reactive groups. The effect of such a silane coupling agent is to increase the bonding strength of the (γ) adhesive layer or the (δ) hardened coating layer. Among these, a silane coupling agent having an amino group is preferred from the viewpoint of improving the bonding strength.

The coating material containing the silane coupling agent may be a coating material containing a silane coupling agent as a main component (solid content of 50% by mass or more). The silane coupling agent preferably has a solid content of 75% by mass or more, and more preferably 90% by mass or more.

Examples include N-2- (aminoethyl) -3-aminopropyl, N-2- (aminoethyl) -3-propyltrimethoxysilane, and N-2- (aminoethyl) -3 -Aminopropyltriethoxy, 3-propyltrimethoxysilane, 3-aminopropyl, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-propyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxy, and the like are used as the silane coupling agent containing the aforementioned amino group. One or more of these mixtures can be used as the silane coupling agent having the aforementioned amino group.

The method for forming the above-mentioned thickened coating using the above-mentioned thickened coating agent is not particularly limited, and a conventional method may be used. Specific examples include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air-knife-coat, and die coating. At this time, any diluent solvents such as methanol, ethanol, isopropanol, 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, and methyl isobutyl can be used as required. Ketone, ethyl acetate, acetone and the like.

In addition, the above-mentioned tackifier coating agent may also contain one or more antioxidants, weather-resistant stabilizers, light-resistant stabilizers, ultraviolet absorbers, and thermal stabilizers as long as they do not violate the purpose of the present invention. , Antistatic agents, surfactants, colorants, infrared shielding agents, leveling agents, additives with thixotropic tackifiers and fillers.

The thickness of the above thickening coating is usually 0.01 to 5 μm, and preferably 0.1 to 2 μm.

(γ) Adhesive layer

The (γ) adhesive layer is a layer composed of a composition containing an adhesive (hereinafter sometimes referred to simply as "adhesive").

The (γ) adhesive layer may be formed on both sides of the (α) poly (meth) acrylimide resin film layer. That is, the adhesive film of the present invention may have (γ) the second adhesive layer, the (α) poly (meth) acrylimide resin film layer, and (γ) the first adhesive layer in this order from the surface layer side.剂 层。 The agent layer. The (γ) second adhesive layer may further include a (α) poly (meth) acrylimide resin film layer. That is, the adhesive film of the present invention can also be sequentially It has (α) the second poly (meth) acrylimide resin film layer, (γ) the second adhesive layer, (α) the first poly (meth) acrylimide resin film layer, and ( γ) The first adhesive layer. The first adhesive layer and the second adhesive layer may be the same or different, but preferably the same. The first poly (meth) acrylimide resin film layer and the second poly (meth) acrylimide resin film layer may be the same or different, but they are preferably the same.

In view of the purpose of using the adhesive film of the present invention as a member for an image display device, the adhesive used to form the (γ) adhesive layer is not limited except for its excellent transparency. The adhesive is preferably excellent in transparency and no coloring. Conventional acrylic, polyurethane, rubber and silicone adhesives can be used as the adhesive.

In the present specification, the "adhesive with good transparency" means an adhesive whose visible light transmittance is 80% or more, preferably 85% or more, and more preferably 90% or more. Here, the visible light transmittance is assumed to be the integral of the transmission spectrum under the condition that the transmittance is 100% in the entire range of the wavelength from 380 to 780 nanometers in the adhesive spectrum. The calculated value of the area ratio. Among them, this adhesive uses a spectrophotometer "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation and a quartz cell with a light path length of 10 mm. And the determination.

In the present specification, the "adhesive with excellent non-coloring property" means that the yellowness index is 3 or less, preferably 2 or less, and an adhesive of 1 or less is the most preferable. Here, the yellowness index is based on JIS K7105: 1981 and uses a colorimeter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation. Product name) and the value measured by a quartz cell with a light path length of 10 mm.

When the adhesive film of the present invention is used as a display panel, an acrylic adhesive is preferred from the viewpoint of light resistance and heat resistance. The acrylic adhesive is composed of an acrylic polymer and an adhesive composition for responding to any desired component.

Examples of the acrylic polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentane (meth) acrylate. Base, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid (Meth) acrylate monomers such as dodecyl, tetradecyl (meth) acrylate, cetyl (meth) acrylate, and octadecyl (meth) acrylate; acrylic acid, methacrylic acid, Itaconic acid, β-carboxyethyl (meth) acrylate and other carboxyl group-containing monomers; glyceryl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether and other epoxy groups Monomer; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) ) Polymers or copolymers of 3-hydroxybutyl acrylate and a mixture of one or two or more hydroxy (meth) acrylate monomers such as 4-hydroxybutyl (meth) acrylate and the like Thereof. The (meth) acrylate means an acrylate or a methacrylate. These acrylic polymers may be used as a mixture of one or more of them.

For example, a silane coupling agent, a compound having two or more epoxy groups in one molecule, A compound having two or more isocyanate groups in one molecule, a photoinitiator, an organic polyvalent metal compound, an antistatic agent, a surfactant, a thixotropic agent, an antifouling agent, and a printability improver, Antioxidants, weather-resistant stabilizers, light stabilizers, ultraviolet absorbers, heat stabilizers, pigments and fillers, etc. are used as any of the above-mentioned components that can be used in acrylic adhesives. The blending amount of the above-mentioned optional components may be set to about 100 to about 10 parts by mass of the acrylic polymer.

When the adhesive film of the present invention is used to protect the adhesive film on the surface of a display panel, it will never be sucked into the air and will be affixed to a person's hand (such as “non-bubble”). No external force is applied to the film, and it will not shift or peel off after long-term use in an environment that includes temperature changes (hereinafter referred to as "maintenance reliability"); and it will not leave adhesive on hands when changing and pasting. From the standpoint that a change in the appearance of the adhesive film can be caused to peel (hereinafter referred to as "appearance protection at the time of peeling"), a silicon adhesive is preferred.

It is not particularly limited as the above-mentioned silicon adhesive, but any one of a reaction-type silicon adhesive and a peroxide-hardened silicon adhesive may be used. The above-mentioned addition reaction type silicon adhesive is an addition reaction of an organic silicon polymer which can be additionally reacted with a vinyl group, a platinum compound such as chloroplatinic acid, a rhodium complex and a ruthenium complex. Catalysts; and adhesive compositions containing any ingredients used as desired. The above-mentioned peroxide-hardening type silicon adhesive is a silicon polymer, an organic peroxide such as benzoyl peroxide, and an adhesive composition containing any component used as desired.

Examples include antistatic agents, surfactants, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather-resistant stabilizers, light stabilizers, ultraviolet absorbers, heat stabilizers, pigments, and fillers. ) And the like as any of the above-mentioned components that can be used in a silicone adhesive. The compounding quantity of the said arbitrary component can also make the said silicon polymer into 100 mass part and about 0.01-10 mass part.

The method for forming the (γ) adhesive layer on at least one side of the poly (meth) acrylimide resin film using the above-mentioned adhesive is not particularly limited, and any wet coating can be used. Examples include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air-knife-coat, and die coating. In addition, when forming the layer (γ), for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate can also be used. acetate), isopropanol, 1-methoxyl (propok), 2-propanol, methanol, ethanol, toluene, xylene and acetone.

There is no particular limitation on the thickness of the (γ) adhesive layer, and if a conventional wet coating method is considered, it is usually 0.5 to 200 μm, preferably 1 to 120 μm, and most preferably 5 to 50 μm.

(δ) Hardened coating layer

The adhesive film of the present invention preferably has a (δ) hardened coating layer on the surface layer side of the (α) poly (meth) acrylimide resin film layer. Improves wear resistance and surface hardness.

The (δ) hardened coating layer may be formed on the (α) poly (meth) acrylimide resin. Both sides of the film layer. That is, the adhesive film of the present invention may also have, in order from the surface layer side, (δ) the first hardened coating layer, (α) the poly (meth) acrylimide resin film layer, and (δ) the first Second, the hard coating layer and the (γ) adhesive layer. In addition, in addition to the (α) poly (meth) acrylimide resin film layer having a (δ) hardened coating layer formed on the upper surface, a structure having a (γ) adhesive layer formed on the upper surface may be formed. (α) Poly (meth) acrylimide resin film layer. For example, the adhesive film of the present invention may have, in order from the surface layer side, (δ) a hardened coating layer, (α) a second poly (meth) acrylimide resin film layer, and (γ) a second adhesive layer. The agent layer is (α) the first poly (meth) acrylimide resin film layer and (γ) the first adhesive layer.

Although the first poly (meth) acrylimide resin film layer and the second poly (meth) acrylimide resin film layer may be the same or different, they are preferably the same. Although the first adhesive layer and the second adhesive layer may be the same or different, they are preferably the same. The first poly (meth) acrylimide resin film layer and the second poly (meth) acrylimide resin film layer may be the same or different, but they are preferably the same.

In view of the purpose of using the adhesive film of the present invention as a member for an image display device, there is no limitation as to a coating material for forming the (δ) hardened coating layer, except that it has good transparency. The coating for forming a hardened coating layer is preferably one having excellent transparency and non-coloring properties. "Good transparency" and "Good coloring resistance" here are based on the above description of these characteristics of the adhesive. An active energy ray-curable resin composition is mentioned as a preferable coating material for hardening coating layer formation.

The active energy ray-curable resin composition can be polymerized and cured by active energy properties such as ultraviolet rays or electron rays to form a hardened coating. To be an active energy ray hardening tree Examples of the lipid composition include a compound containing an active energy ray-curable resin and further containing two or more isocyanate groups (-N = C = O) per molecule and / or a photoinitiator.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate), polyacrylic acid, (Meth) acrylate (Polyacrylic (meth) acrylate), polyepoxy (meth) acrylate, polyalkyleneglycol poly (meth) acrylate (meth) acrylate) and polyether (meth) acrylate and other prepolymers or oligomers containing (meth) acryloyl; methyl (meth) acrylate (methyl (meth) acrylate), ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate ( hexyl (meth) acrylate), ethylhexyl (meth) acrylate, sodium (meth) acrylate, (meth) acrylate isobornyl ( isobornyl (meth) acrylate), dicyclopentenyl (meth) acrylate, dicyclopentenylene (meth) acryla te), phenyl (meth) acrylate, phenylcellosolve (meth) acrylate, and methoxyethyl 2- (meth) acrylate (methoxyethyl (meth) acrylate), hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 2-acryloyloxyhydrophthalate Formate (acryloyloxypropyl hexa hydro hydrogenphosphite phthalate), dimethylaminoethyl (meth) acrylate, trifluoro (meth) acrylate Monofunctional reactive monomers containing (meth) propenyl groups, such as trifluoroethyl (meth) acrylate and trimethylsilyloxy ethyl methacrylate; N-vinylpyrrolidone, styrene ( Monofunctional reactive monomers such as styrene); diethylene di (meth) acrylate, neopentyl glycol (meth) acrylate , 1,6-hexanediol (meth) acrylate, polyethylene glycol (meth) acrylate, 2,2'-bis ( 4- (meth) acryloyloxy polyethyleneoxy propane, 2,2'-bis (4- (meth) acryloyloxy polypropyleneoxyphenyl) propane (Meth) acryloyl-containing bifunctional reactive monomers; trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (Meth) acryloyl-containing trifunctional reactive monomers such as trimethylol ethane tri (meth) acrylate; pentaerythritol tetra (methyl (Meth) acryloyl-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and (meth) acryloyl containing poly (dipentaerythritol hexaacrylate) Six or more functional reactive monomers are selected from one or more resins, or one or more of the above resins are used as constituent monomers. One or two or more of these mixtures can be used as the active energy ray-curable resin.

In addition, in this specification, (meth) acrylic acid means an acrylate or a methacrylate.

As a compound having two or more isocyanate groups in one molecule, for example, Out: methylenebis-4-cyclohexy isocyanate; trimethylolpropane of tolylene diisocyanate, trimethylolpropane of hexamethylene diisocyanate Trimethylolpropane, trimethylolpropane isophorone diisocyanate, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate (hexamethylene diisocyanate) isocyanurate (isocyanurate), isophorone diisocyanate (isocyanurate), hexamethylene diisocyanate (hexamethylene diisocyanate) biuret and other polyisocyanates (polyisocyanate); and urethane crosslinking agents such as the block isocyanate of the above-mentioned polyisocyanate. These can also be used individually or in combination of 2 or more types. In addition, at the time of crosslinking, catalysts such as dibutyltin dilaurate, dibutyltin ethylhexoate and the like can be added according to demand.

Examples of the photoinitiator include benzophenone, methyl-0-benzoyl benzoate, and 4-methylbenzophenone. ), 4,4'-bis (diethylamino) benzophenone, 0-methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzene Benzoyl-4'-methydiphenyl sulfide, 3,3 ', 4,4'-tert-butyl peroxycarbonyl benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as benzoin diethyl ether, benzoin isopropyl ether, benzil methyl ketal; acetophenone, 2,2-dimethoxy Acetophenone compounds such as -2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone; methylanthraquinone, 2-ethylanthraquinone (anthraquinone) compounds such as ethylanthraquinone, amylanthraquinon; thioxanthone, 2,4-diethylthioxantone, 2,4-diisopropylthione Dilsopropylthioxanthone and other thioxanthone compounds; acetophenone dimethyl acetal and other alkyl phenones compounds; triazon compounds; biimidazole ) Compounds, acylphosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime ester phenylacetate compounds; hydroxyketones And was aminobenzoate (aminobenzoate) compound. These can also be used individually or in combination of 2 or more types.

The (δ) hardened coating layer preferably comprises: (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) having alkoxysilyl and (methyl) Acryloyl compound 0.2 to 4 parts by mass; (C) organic titanium 0.05 to 3 parts by mass; and (D) 5 to 100 parts by mass of active energy ray-curable resin composition of fine particles having an average particle diameter of 1 to 300 nm . (δ) The hardened coating layer is more preferably composed of: (A) 100 parts by mass of polyfunctional (meth) acrylate; (B) having alkoxysilyl and (meth) acryloyl 0.2 to 4 parts by mass of compound; (C) 0.05 to 3 parts by mass of organic titanium; (D) having an average particle diameter of 1 to 300 nm 5 to 100 parts by mass of microparticles; and (E) an active energy ray-curable resin composition composed of repellents of 0.01 to 7 parts by mass. By allowing the (δ) hardened coating layer to have such a composition, regardless of its transparency, hue, abrasion resistance, surface hardness, bending resistance, and surface appearance, it can be wiped repeatedly with a handkerchief or the like. An adhesive film capable of maintaining surface characteristics such as slipperiness was obtained.

(A) Multifunctional (meth) acrylate

The said component (A) has 2 or more (meth) acryloyl (meth) acrylates in 1 molecule. Since this component has two or more (meth) acryloyl groups in one molecule, its function is to form a hardened coating by polymerizing and hardening the active energy of ultraviolet rays or electron rays.

Examples include: diethylene glycol dimethacrylate, neopentylglycol dimethacrylate, 1,6-hexanediol di (meth) acrylate ( hexanediol (meth) acrylate), polyethylene glycol (meth) acrylate, 2,2'-bis (4- (meth) acryloyl polyvinyloxy ((meth) (methryacryloyloxy polyethyleneoxy) propane, (meth) acryloyloxy polypropyleneoxyphenyl (meth) acryloyl-containing bifunctional reactive monomers such as (meth) acryloyloxy polypropyleneoxyphenyl ; Trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, etc. ) Trifunctional reactive monomer of propylene; (methyl) containing polypentaerythritol hexaacrylate 4-functional reactive monomers of propylene; (meth) propylene-containing 6-functional reactive monomers, such as polypentaerythritol hexaacrylate, and polymers (oligosaccharides) that use one or more of these as constituent monomers Polymers (oligomers or prepolymers) are used as the above-mentioned multifunctional (meth) acrylates. As the component (A), one kind or a mixture of two or more kinds of these may be used.

(B) Compounds having alkoxysilyl and (meth) acryloyl

The function of the above-mentioned component B can be in the molecule. By having a (meth) acryloyl group, the above-mentioned component A and the alkoxysilyl group can be used to chemically combine or strongly interact with the above-mentioned component D, thereby greatly improving the hardening coating. Abrasion resistance of cloth. In addition, the function of the above-mentioned component B can be that the component E can be chemically bound or strongly interacted by having a (meth) acryloyl group or by having an alkoxysilyl group in the molecule, which can prevent the component E from exuding Wait for the trouble event. Here, (meth) acryloyl means acryloyl or methacryloyl.

The component B is different from the component A in that it has an alkoxysilyl group. The compound of the aforementioned component A does not have an alkoxysilyl group. In the present specification, a compound-based component B having an alkoxysilyl group and two or more (meth) acryloyl groups in one molecule.

For example, a compound having a chemical structure represented by the general formula (-SiO ₂ RR'-) _n ‧ (-SiO ₂ RR "-) _m may be used as the component B. Here, n is a natural number (a positive integer) ), M is 0 or a natural number. N is preferably a natural number of 2-10, and m is a natural number of 0 or 1 to 10. R is a methoxy group (CH ₃ O-), and an ethoxy group (C ₂ H ₅ O-), etc. R 'is acryl (CH ₂ = CHCO-), methacryl (CH ₂ = C (CH ₃ ) CO-). R "is methyl (CH ₃ ), ethyl (CH ₂ CH ₃ ) and the like.

May include for example having the general formula _{"(-SiO 2 (OCH 3) (} OCHC = CH 2) -) n ", _{"(- SiO 2 (OCH 3)} (OC (CH 3) C = CH 2) -) _n "," (-SiO ₂ (OCH ₃ ) (OCHC = CH ₂ )-) _n ‧ (-SiO ₂ (OCH ₃ ) (CH ₃ )-) _m "," (-SiO ₂ (OCH ₃ ) (OC (CH ₃ ) C = CH ₂ )-) _n ‧ (-SiO ₂ (OCH ₃ ) (CH ₃ )-) _m '', "(-SiO ₂ (OC ₂ H ₅ ) (OCHC = CH ₂ )-) _n "," (-SiO ₂ (OC ₂ H ₅ ) (OC (CH ₃ ) C = CH ₂ )-) _n "," (-SiO ₂ (OC ₂ H ₅ ) (OCHC = CH ₂ )-) _n ‧ (-SiO ₂ (OCH ₃ ) (CH ₃ )-) _m '', and A compound of the chemical structure shown in (-SiO ₂ (OC ₂ H ₅ ) (OC (CH ₃ ) C = CH ₂ )-) _n ‧ (-SiO ₂ (OCH ₃ ) (CH ₃ )-) _m ) As the aforementioned component B. Here, n is a natural number (positive integer), and m is 0 or a natural number. n is preferably a natural number of 2-10, and m is a natural number of 0 or 1-10.

As the above-mentioned component B, one kind or a mixture of two or more kinds of these may be used.

The blending amount of the component B is 0.2 mass part or more, more preferably 0.5 mass part or more, and more preferably 1 mass part or more, from the viewpoint of abrasion resistance of the mass part of the component A100. In addition, from the viewpoint of easily discovering a water-repellent agent, and from the viewpoint that the blending ratio of the above-mentioned component B and the above-mentioned component C is within a preferred range without excessively increasing the amount of the above-mentioned component C, the blending amount of the above-mentioned component B is 4 The mass part is preferably 3 mass parts or less, and more preferably 2 mass parts or less.

In addition, from the viewpoint of chemically bonding or interacting strongly with the component D, The compounding ratio of the component B and the component D is preferably 0.5 to 15 mass portions, and more preferably 2 to 7 mass portions relative to the mass portion of the component D100.

(C) organic titanium

The component C is a component for assisting the function of the component B. From the viewpoint of significantly improving the abrasion resistance of the hard coating, the component B and the component C represent a peculiarly good chemical reaction. In addition, the function of the component C itself can also be chemically combined with or strongly interact with the above-mentioned component D and the like, and has improved abrasion resistance of hard coating.

Examples of the organic titanium include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra- (2-ethylhexyloxy) titanium, and titanium-i. -propoxyoctyleneglycolate, di-i-propoxy‧bis (acetylacetonate) titanium, propanediyldioxytitanium bis (ethyl acetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxy titanium Stearate (propoxy titanium distearate), titanium distearate, di-i-propoxy titanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, di-n-butoxy-bis ( triethanolaminato) and a polymer formed from one or more of these. As the component C, one or two or more of these mixtures can be used.

Among these, from the viewpoints of wear resistance and hue, tetra-i-propoxy titanium, tetra-n-butoxy titanium, and tetra- (2-ethylhexyloxy) titanium and titanium-i-propoxyoctyleneglycolate.

The compounding quantity of the said component C is 0.05 mass part or more from a viewpoint of abrasion resistance with respect to the said A100 mass part, Preferably it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more. From the viewpoint of color tone, the blending amount of the component C is 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1.5 parts by mass.

In addition, from the viewpoint of effectively assisting the effect of the component B, the blending amount of the component B and the component C is 5 to 150 mass parts, and more preferably 20 to 80, relative to the mass part of the component B 100. Quality Department.

(D) Fine particles with an average particle diameter of 1 to 300 nm

The effect of the aforementioned component D is to increase the surface hardness of the hard coating. In addition, its interaction with the aforementioned component A is weak and it also causes a cause of insufficient abrasion resistance. Therefore, in the present invention, the above-mentioned component B that can chemically bond or strongly interact with the above-mentioned component A and the above-mentioned component D and the above-mentioned component C that can assist the action of the component B will be used to solve this problem.

Therefore, the component D is preferably a substance that can be chemically combined or strongly interacted with the above-mentioned component B, and more preferably a substance that can be chemically combined or strongly interacted with the above-mentioned component B and the above-mentioned component C.

Either inorganic fine particles or organic fine particles may be used as the component D. Examples of the inorganic fine particles include silica (silicon dioxide), alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, and antimony oxide. Fine metal oxide particles such as cerium oxide; fine metal oxide particles such as magnesium fluoride and sodium fluoride; fine metal sulfide particles; fine metal nitride particles; fine metal particles and the like. As organic particles Examples thereof include resin beads such as styrene resin, acrylic resin, polycarbonate resin, ethylene resin, amino compound, and hardened resin of formaldehyde. These can be used individually by 1 type or in combination of 2 or more types.

As any of these substance groups listed as the component D, a substance that can at least chemically bond or strongly interact with the component B should be considered.

In addition, for the purpose of improving the dispersibility in the coating of fine particles or increasing the surface hardness of the hardened coating layer obtained, the surface of the fine particles can also be made of: vinyl silane, amino silane (aminosilane) and other silane coupling agents; Titanate coupling agent; aluminate coupling agent; (acryloyl), vinyl (vinyl), allyl (allyl), organic compounds such as ethylenically unsaturated binding groups or reactive functional groups such as epoxy groups; surface treatment agents such as fatty acids, fatty acid metal salts, and the like.

Among these, in order to obtain a hardened coating having a higher surface hardness, fine particles of silicon or alumina are preferable, and among these, fine particles of silicon are most preferable. The silicon particles currently on the market are: SONO-TEK (trade name) by Nissan Chemical Co., and Quotron (trade name) by Fuso Chemical Co., etc.

The average particle diameter of the component D is preferably 300 nm or less from the viewpoint of maintaining the transparency of the hard coating and the effect of improving the surface hardness of the hard coating. The upper limit of the average particle diameter of the component D is preferably 200 nm or less, and more preferably 120 nm or less. In addition, although there is no particular limitation on the lower limit of the average particle diameter of the component D, the particles that can usually be obtained are usually about 1 nm even as fine as possible.

In addition, in this specification, the average particle diameter of the fine particles is based on the use of laser diffraction by Nikkiso Co., Ltd. of Japan. In the particle diameter distribution curve measured by the scattered particle size analyzer "MT3200II (trade name)", the smaller particles accumulate to 50% by mass of the particle diameter.

The blending amount of the component D is 5 parts by mass or more, and preferably 20 parts by mass or more, from the viewpoint of surface hardness with respect to the mass part of the component A100. From the viewpoint of abrasion resistance and transparency, the blending amount of the component D is 100 parts by mass or less, preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

(E) Water repellent

The active energy ray-curable resin composition preferably further contains 0.01 to 7 parts by mass of (E) a water-repellent agent from the viewpoints of improving the slipperiness, anti-fouling adhesion, and fouling-wiping property.

Examples of the water-repellent agent include wax-repellent agents such as paraffin wax, polyethylene wax, acrylic resin and ethylene copolymer wax; silicone oil, silicone resin, polydimethylsiloxane; alkylalkoxysilane, etc. Silicon water repellent; fluoropolyether water repellent and fluoropolyalkyl water repellent. As the component E, a mixture of one or more of these may be used.

Among these, from the viewpoint of water repellency, a fluoropolyether water repellent is preferred. From the viewpoint of allowing the component A or the component B to chemically bond or strongly interact with the component E, and to prevent the component E from oozing out, it is best that the molecule contains a (meth) acryloyl group and a fluoropolyether group. A compound water-repellent agent (hereinafter referred to as (meth) acryloyl-containing fluoropolyether water-repellent agent) is used as the component E.

In addition, if component A or component B and component E are chemically combined or appropriately adjusted and interacted, from the viewpoint of high transparency and good water repellency can be found at the same time, acryl-containing fluoropolyether can be used for water repellence. As a component E, a mixture of an agent and a fluoropolyether water-repellent agent containing methacryloyl group.

When the component E is used, the blending amount thereof is generally 7 mass parts or less, and preferably 4 mass parts or less, from the viewpoint of preventing the component E from oozing out. The lower limit of the blending amount of the component E may be any component, so there is no particular limitation, but from the viewpoint of obtaining a desired effect, it is usually 0.01 mass part or more, preferably 0.05 mass part or more, and more preferably 0.1 mass part or more.

The aforementioned components A to D are preferably active energy ray-curable resin compositions containing the aforementioned components A to E, and from the viewpoint of being able to make a good curability by active energy rays, it is preferably 1 The compound further contains two or more isocyanate groups (-N = C = O) and / or a photoinitiator.

The above-mentioned active energy ray-curable resin composition may also contain one or more antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, and antioxidants as required. , Weather-resistant stabilizer, light stabilizer, ultraviolet absorber, heat stabilizer, colorant, filler and other additives.

Since the above-mentioned active energy ray-curable resin composition is to be diluted to a relatively easy-to-apply concentration, a solvent may be blended as desired. The solvent is not particularly limited as long as it does not react with the components of the composition or does not catalyze (promote) the self-reactions (including deterioration reactions) of these components. Examples of the solvent include 1-methoxyl-2-propanol, ethyl acetate, butyl acetate, toluene, and methyl ethyl ketone ( methyl ethyl ketone), methyl isobutyl ketone, diacetone alcohol, acetone, and the like.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

There is no particular limitation on the method for forming the (δ) cured coating layer by using the coating material for hardened coating formation containing the above active energy ray-curable resin composition, and a conventional wet coating method may be used. Specific examples include methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air-knife-coat, and die coating.

Although the thickness of the (δ) hardened coating layer is not particularly limited, from the viewpoints of rigidity, heat resistance and dimensional stability of the adhesive film of the present invention, it is usually 1 μm or more, preferably 5 μm or more, and more preferably It is preferably 10 μm or more, and more preferably 15 μm or more. From the standpoint of machinability or wet handling of the adhesive film of the present invention, it is preferably 100 μm or less and more preferably 50 μm or less.

The adhesive film of the present invention has a total light transmittance (measured in accordance with JIS K7361-1: 1997 and measured using a turbidimeter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.) of 80% or more. With a total light transmittance of 80% or more, the adhesive film of the present invention can be preferably used as a component of an image display device. The higher the total light transmittance, the better, preferably 85% or more, more preferably 88% or more, and most preferably 90% or more.

The yellowness index of the adhesive film of the present invention (measured in accordance with JIS K7105: 1981 and using a colorimeter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation) is preferably 3 or less, and 2 or less is more Good, 1 is the best. The lower the yellowness index, the better. By having such a yellowness index, the adhesive film of the present invention can be preferably used as a component of an image display device.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

Physical determination. Evaluation method

(i) No bubbles

From the adhesive film, a test piece having a size of 30 cm in the longitudinal direction and 20 cm in the horizontal direction was used to make the mechanical direction of the poly (meth) acrylimide resin film layer constituting the adhesive film layer (α) the longitudinal direction of the test piece. From one end in the horizontal direction to the vertical direction and using a human hand, apply the test piece to a glass plate that is placed on a table (JIS Test Paper Co., Ltd. JIS R3202: 2011, a thickness of 3mm). (Float glass, the same below). At this time The appearance was evaluated for the presence of air bubbles, bulging, and other appearance defects, and was evaluated on the following criteria.

○ (Good): There is no swelling due to inhalation of air bubbles.

△ (Slightly defective): There is a phenomenon of bulging due to inhalation of air bubbles. However, it is easy to squeeze out air bubbles without swelling from above the film by squeezing with fingers.

×: (Bad): There is a phenomenon of bulging due to inhalation of air bubbles. However, even if a finger is pressed from above the film, a bulging phenomenon of no bubbles will occur.

(ii) Maintenance reliability

As in the above experiment (i), the sample with the adhesive film attached to the glass plate was exposed to a temperature of -40 ° C for 30 minutes using a hot and cold impact tester (without temperature control mechanism), followed by exposure to a temperature of 80 ° C. The processing of the environment is set to one cycle, and 13 cycles are performed. After the treatment, the samples were visually observed and evaluated on the following criteria.

○ (Good): The adhesive film does not float from the glass plate (where the adhesive film peels off from the glass plate).

△ (slightly defective): The adhesive film was raised from the glass plate at the end of the adhesive film.

×: (Bad): There was a phenomenon that the adhesive film floated from the glass plate as a whole.

(iii) appearance protection at the time of peeling

Similar to the above-mentioned experiment (i), after the adhesive film was stuck on the glass plate, the adhesive film was peeled off from the glass plate by a human hand, and the evaluation was performed on the following criteria.

○ (Good): There is no adhesive residue and the film can be easily peeled off. The film will not bend or plastically deform.

△ (Slightly bad): No adhesive residue and peelable film. However, the film is bent or plastically deformed.

X: (bad): Adhesive phenomenon was observed when the film was peeled. In addition, the film may be bent or plastically deformed.

(iv) Total light transmittance

The total light transmittance of the adhesive film was measured in accordance with JIS K7361-1: 1997 and using a turbidimeter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.

(v) Yellowness index

The yellowness index of the adhesive film was measured in accordance with JIS K7105: 1981 and using a colorimeter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation. If the yellowness index is 3 or less, it is evaluated as good, if it is more than 3 and less than 4, it is evaluated as slightly good, and if it exceeds 4, it is evaluated as bad.

Used raw materials

Poly (meth) acrylimide resin film

(α-1) Using the co-extrusion film-forming apparatus shown in FIG. 1 and using extruder 1 as a transparent multilayer film, poly (meth) acrylimide “PLEXIMID TT70” (trade name) of Japan's EVONIK Co., Ltd. The two outer layers (α1 layer and α2 layer), and the aromatic polycarbonate "CALIBRE-301-4" (trade name) of Sumika Styron Polycarbonate Limited of Japan as the middle layer of the transparent multilayer film (β Layer), so that the melted film 4 of the transparent multilayer film laminated directly in the order of α1 layer, β layer and α2 layer can be continuously extruded from two types of three-layer multi-manifold co-extrusion T-die 3 Let the α1 layer be the mirror roller 5 side, and supply the input and feed between the rotating mirror roller 5 and the mirror conveyor belt circulating along the peripheral surface of a pair of conveyor rollers 7. A thin transparent resin film with a good surface appearance can be obtained by squeezing, with a thickness of 125 μm, a layer thickness of α1 layer of 40 μm, a layer thickness of β layer of 45 μm, and a layer thickness of α2 layer of 40 μm. The setting conditions at this time are: the drying temperature (α-1) before film formation is 150 ° C and (β-1) is 100 ° C; the setting temperature of the extruder 1 is C1 / C2 / C3 / C4 / C5 / AD = 260/290 ~ 290 ℃; the temperature of extruder 2 is set to C1 / C2 / C3 / C4 / C5 / C6 / AD = 260/280/280/260 ~ 260/270 ° C; for any extruder 1 or 2 Perform nitrogen purging and use a vacuum vent; the set temperature of the T-die 3 is 300 ° C, and the lip opening is 0.3mm; the set temperature of the mirror roller 5 is 130 ° C, and the set temperature of the mirror conveyor 6 is 120 ° C. The down pressure is 1.4 MPa, and the take-over speed is 9.8 m / min. The total light transmittance, haze value and yellowness index of the obtained transparent multilayer film were measured. The results are shown in Table 1.

(α-2) ~ (α-12): Except changing any one or more of the temperature of the mirror roller 5, the temperature of the mirror conveyor belt 6, and the thickness of each layer to Table 1 or Table 2, the rest will be the same as above (α -1) A transparent resin film with a good surface appearance can be obtained. The total light transmittance, haze value and yellowness index of the obtained transparent multilayer film were measured. The results are shown in Table 1 or Table 2.

(α-13): In addition to changing the overall thickness to 500 μm, the layer thickness of the α1 layer to 40 μm, the layer thickness of the β layer to 340 μm, the layer thickness of the α2 layer to 80 μm, and the take-over speed (take-over speed) is 3.3m / min, the lip opening is 1mm, the rest will be the same as (α-1) above, and a transparent resin film with a good surface appearance can be obtained. The total light transmittance, haze value and yellowness index of the obtained transparent multilayer film were measured. The results are shown in Table 2.

(α-14): Poly (meth) acrylimide "PLEXIMID" from Japan's EVONIK "TT70" (trade name), and equipped with a 50mm extruder (equipped with W / L = 29, CR = 1.86 W screw); T-die with a mold width of 680nm; on the mirror roller (the first mirror body ) And a mirror conveyor belt (second mirror body) to squeeze the device of the winding machine of the melting film mechanism, a film with a good surface appearance of 250 μm in thickness can be obtained. The setting conditions at this time, the temperature of the extruder is set to C1 / C2 / C3 / AD = 280/300/320/320 ° C; the set temperature of the T-die is 320 ° C; the lip opening of the T-die is 0.3mm The set temperature of the mirror roller is 130 ° C; the set temperature of the mirror conveyor is 120 ° C; the pressure under the mirror conveyor is 1.4MPa; the take-over speed is 8.7m / min. The obtained film was measured for total light transmittance, haze value and yellowness index. The results are shown in Table 2.

(γ) Adhesive

Mixing and Stirring (γ-1) Shin-Etsu Chemical Industry Co., Ltd.'s additive reaction type silicon adhesive "KR-3704" (trade name) 100 mass division, Shin-Etsu Chemical Industry Co., Ltd.'s platinum compound additive reaction catalyst "CAT- "PL-50T" (trade name) 0.5 mass part and toluene 20 mass part can be obtained.

Example 1

On one side of the above (α-1), an adhesive film can be obtained by applying a glue and then coating the above (γ-1) so that the thickness after curing is 30 μm, and heating and curing at 130 ° C. for 1 minute. The above tests (i) to (v) were performed on this adhesive film. The results are shown in Table 1.

Examples 2 to 14

Except that the poly (meth) acrylimide resin film shown in Table 1 or Table 2 was used in place of the above (α-1), the rest were the same as in Example 1. The production of the adhesive film, physical measurement and evaluation were performed. . The results are shown in Table 1 or Table 2.

From the results in Tables 1 and 2, it can be found that the adhesive film of the present invention is preferably used as a physical property of a protective film for a display panel.

test methods

(vi) Water contact angle (initial water contact angle)

The hardened coated surface of the adhesive film was measured using an automatic contact angle meter "DSA20" (trade name) manufactured by KRUSS, and a method calculated from the width and height of water droplets (refer to JIS R3257: 1999).

(vii) Abrasion resistance (water contact angle after wiping cotton cloth)

With a size of 150 mm in the longitudinal direction and 50 mm in the transverse direction, a test piece was taken so that the mechanical direction of the poly (meth) acrylimide resin film constituting the (α) layer of the adhesive film became the longitudinal direction of the test piece. This test piece was placed on a tester of JIS L0849 with a hardened coating surface as a surface, and 4 pieces of gauze were overlapped on the friction terminals of the tester of tester (Kawamoto Sangyo Co., Ltd. Limited company's medical type 1 gauze) stainless steel plate (10mm in length, 10mm in width, 1mm in thickness), set the vertical and horizontal sides of the stainless steel plate to contact the test piece, and on the stainless steel plate covered with the gauze After placing a load of 350g, let the hardened coated surface of the test piece wipe back and forth 20,000 times under the conditions of a friction terminal moving distance of 60mm and a speed of 1 round-trip / second, and then measure the value according to the method (vi) above. Water contact angle of cotton wipes. When the water contact angle is 100 degrees or more, it can be judged that the abrasion resistance is good. In addition, when the water contact angle after 20,000 back-and-forth wipes is less than 100 degrees, measurements are also performed to change the predetermined number of back-and-forth rounds to 15,000 and 10,000 times, and then evaluated based on the following criteria.

◎ (very good): The water contact angle is 100 degrees or more even after 20,000 times of back and forth.

○ (Good): After 15,000 round trips, the water contact angle was 100 degrees or more, but after 20,000 times, the water contact angle was less than 100 degrees.

△ (Slightly bad): After wiping 10,000 times, the water contact angle was 100 degrees or more, but after 15,000 times, the water contact angle was less than 100 degrees.

× (bad): After 10,000 rubs, the water contact angle is less than 100 degrees.

(viii) Finger slip

Evaluate the adhesive film with your index finger up, down, left, right, or circled to see if you can achieve the desired trajectory. Let 10 people perform the test. If you want to track the desired person, it will be 2 points. If you want to track the desired person, it will be 1 point. You cannot catch your finger. For example, if you cannot track the desired person, it will be 0 points. Then count each person. The score is evaluated based on the following criteria.

◎ (very good): 16 ~ 20 minutes

△ (slightly bad): 10 ~ 15 points

× (bad): 0 to 9 points

(ix) Finger slip of cotton cloth

According to the above method (vii), except that the adhesive film after 20,000 times of rubbing was set as a sample, all other tests were performed in the same way as the above (viii) finger slip and the finger slip after the cotton wipe was evaluated.

(x) Abrasion resistance (steel wool resistance)

The hardened coated surface was made the surface, and the adhesive film was placed on a JIS L0849 vibration tester. Next, install # 0000 steel wool on the friction terminal of the vibration tester, load a load of 500g, and rub the surface of the test piece back and forth 100 times. This surface was observed visually, and abrasion resistance (steel wool resistance) was evaluated by the following criteria.

((Very good): No scratches.

(Good): 1 to 5 scratches.

△ (slightly bad): 6 to 10 scratches.

× (bad): 11 or more scratches.

(xi) Coefficient of linear expansion

The linear expansion coefficient of the adhesive film was measured in accordance with JIS K7197: 1991. A thermomechanical analysis device (TMA) "EXSTAR6000 (trade name)" of Seiko Instruments was used. The size of the test piece is 20mm in the longitudinal direction and 10mm in the transverse direction, and the machine direction (MD) of the film is taken as the longitudinal direction of the test piece. The state of the test piece was adjusted to a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5 ° C. for 24 hours. For the purpose, it is not necessary to adjust the state during the measurement of the maximum temperature. The chuck spacing is 10mm, the temperature program is set to 20 ° C and held for 3 minutes, and then the temperature is raised to a program with a temperature of 5 ° C / min to a temperature of 270 ° C. The linear expansion coefficient is calculated from the obtained temperature-test piece length curve, and the low-temperature side temperature is 30 ° C and the high-temperature side temperature is 250 ° C. If the linear expansion coefficient is less than 20 ppm, it is very good, if it is more than 20 ppm and less than 30 ppm, it is good, if it is more than 30 ppm and less than 50 ppm, it is slightly good, and if it is more than 50 ppm, it is bad.

(xii) Minimum bending radius

With reference to JIS K6902's bending formability (Method B), the test piece can be obtained by adjusting the state to 24 hours under the environment of a temperature of 23 ° C ± 2 ° C and a relative humidity of 50 ± 5%. The bending temperature of the test piece was 23 ° C ± 2 ° C, and the bending line was set at a right angle to the mechanical direction of the poly (meth) acrylimide resin film constituting the layer (α) of the adhesive film, and was bent to form a curved surface. Let the hardened coating surface of the adhesive film be outside. Among the forming jigs without cracks, the radius of the front part having the smallest radius of the front part is set as the minimum bending radius.

(xiii) Machinability (state of curved cutting line)

A computer-controlled router planer is used to set a circular cutting hole with a radius of 0.5 mm and a circular cutting hole with a radius of 0.1 mm on the adhesive film. When using the milling cutter at this time, the shape of the tip of the cutting edge is a cylindrical four-blade made of cemented carbide with a nick, and the diameter of the blade can be appropriately selected according to the processing place. Next, the cutting end surface of a cutting hole having a radius of 0.5 mm was observed visually or with a microscope (100 times), and the machinability was evaluated by the following criteria. Similarly, observe the cutting end face of a cutting hole with a radius of 0.1 mm with visual or microscope (100 times), and The machinability was evaluated by the following criteria. In the table, the former result-the latter result are recorded in order.

((Very good): No cracks or fine marks were observed even when observed under a microscope.

○ (Good): No crack even when observed under a microscope. But there are fine marks.

△ (Slightly defective): No cracks even when visually observed. However, cracks were observed under the microscope.

× (defective): Cracks were observed even by visual inspection.

(xiv) Surface smoothness (surface appearance)

While changing the incident angle of light of various fluorescent lamps and touching them, the hardened coating surface of the adhesive film was visually observed, and the surface smoothness (surface appearance) was evaluated according to the following criteria.

((Very good): No bulge or scratch on the surface. There is no turbidity even when looking through the light.

○ (Good): When viewed through light, a slight turbidity is found.

△ (slightly bad): If you look closely, the surface is slightly raised or scratched. In addition, there was a feeling of turbidity.

× (bad): Most of the surface has bumps or scratches. In addition, there was a noticeable cloudiness.

(xv) Pencil hardness

In accordance with JIS K5600-5-4 and a load of 750 g, the pencil "UNI" (trade name) of Mitsubishi Pencil Co., Ltd. was used to measure the pencil hardness of the hardened coated surface of the adhesive film. If the pencil hardness is 6H or more, it is good, if it is 5 or more, it is slightly good, and if it is less than 5H (4H or less), it is bad.

Used raw materials

(A) Multifunctional (meth) acrylate:

(A-1) polypentaerythritol hexaacrylate (6-functional)

(A-2) ethoxy trimethylolpropane triacrylate

(B) Compounds having alkoxysilyl and (meth) acryloyl:

(B-1) Shin-Etsu Silicone KR-513 (trade name: compound represented by (-SiO ₂ RR'-) _n ‧ (-SiO ₂ RR "-) _m , R: (Ethoxy, R ': propenyl, R'': methyl)

(B-2) "Shin-Etsu SiliconX-40-2655A" (trade name) of Shin-Etsu Chemical Industry Co., Ltd. (a compound represented by (-SiO ₂ RR'-) _n ‧ (-SiO ₂ RR "-) _m : R: ethoxy, R 'methacryl: propenyl, R'': methyl)

(B ’) Comparative component

(B'-1) Shin-Etsu Silicone KBM-403 (trade name: Compound with alkoxysilyl and epoxy groups, and no (meth) acryloyl compound)

(B'-2) Shin-Etsu Silicone KBM-903 by Shin-Etsu Chemical Industry Co., Ltd. (Brand name: Compound having alkoxysilyl and amino groups, and not having (meth) acryloyl)

(C) organic titanium

(C-1) titanium-i- (propoxy octylene glycolate) "TOG" (brand name)

(C-2) Tetrakis (2-ethylhexyl) titanium "TOG" (brand name)

(C-3) Di-propoxy of Japan Soda Co., Ltd. bis (acetylacetone) titanium `` TOG '' (brand name)

(C ’) Comparative component:

(C’-1) Tetra-n-propoxyzirconium "ZAA" (trade name)

(D) Fine particles with an average particle diameter of 1 to 300 nm

(D-1) Silicon fine particles with an average particle diameter of 20 nm

(E) Water repellent

(E-1) Acryl-containing fluoropolyether water-repellent agent "KY-1203" (trade name) of Shin-Etsu Chemical Industry Co., Ltd.

(E-2) Japan's Solvay company's methacryl-containing fluoropolyether water repellent "FOMBLIN MT70" (brand name)

(E-3) Acryloyl-containing fluoropolyether water repellent `` megafuatsuku RS-91 '' (brand name) of DIC Corporation

Any other ingredient

(F-1) phenylketon photoinitiator (1-hydroxycyclohexyl phenylketone) `` SB-PI714 '' (brand name)

(F-2) 1-methoxy (propane) propane

(F-3) Surface Conditioner "BYK-399" (Trade Name) of BYK Japan Co., Ltd.

(F-4) hydroxyketone photoinitiator (α-hroxyakylphenones) `` IRGACURE127 '' (trade name) from BASF Japan

(ε) Coating for forming hardened coating on printing surface side

(ε-1) Above (A-1) 65 quality parts, above (A-2) 35 quality parts, above (B-1) 1.4 quality parts, above (C-1) 0.7 quality parts, top (D-1) 35 mass parts, above (F-1) 5.3 mass parts, above (F-2) 9.5 mass parts and above (F-3) 0.5 mass parts are mixed and mixed and mixed And use the resulting paint.

(α ') Comparative film substrate

(α'-1) A biaxially stretched polyethylene terephthalate film "DIAFOL" (trade name) of Mitsubishi Pencil Co., Ltd. was used, and the thickness was 125 m.

(α'-2) An acrylic resin film "TECHNOLLOY S001G" (trade name) of Sumitomo Chemical Co., Ltd. was used, and the thickness was 125 m.

(α'-3) Japan's Sumika Styron Polycarbonate Limited's aromatic polycarbonate "CALIBRE-301-4" (trade name) is used, and a 50mm press (equipped with L / D = 29, CR = W screw 1.86); T-die with a mold width of 680nm; on a mirror roller (first mirror surface) Body) and a mirror conveyor (second mirror body) to squeeze the device of the winding machine of the molten film mechanism, and a film having a thickness of 250 μm can be obtained. The setting conditions at this time, the temperature of the extruder is set to C1 / C2 / C3 / AD = 280/300/320/320 ℃; the set temperature of the T-type mold is 320 ℃; The set temperature of the mirror roller is 140 ° C; the set temperature of the mirror conveyor is 120 ° C; the pressure under the mirror conveyor is 1.4MPa; the take-over speed is 9.0m / min.

Example 15

The treatment of tip discharge was performed on both sides of the above (α-1) with a processing capacity of 167W · min / m ² (discharge power is 500W, the length of the discharge electrode is 1m, and the production line speed is 3m / min). The wetness index on both sides is 64mN / m. Next, on the side of the α1 layer, a coating device using a mold method was used, and the coating material with the composition (quality portion) shown in Table 3 was used as the coating for the hardening coating on the touch surface side. The thickness is 15 μm; on the side of the α2 layer, a coating device using a mold method is used to apply the coating material for the hardening coating forming (ε-1) on the printing surface side so that the thickness after curing is 15 μm to obtain a cured coating laminated film. Next, on the hardened coating layer on the printing surface side, the above-mentioned (γ-1) was coated with a glue to make the thickness after hardening to be 30 μm, and heated and hardened at 130 ° C. for 1 minute to obtain an adhesive film. The obtained adhesive films were subjected to the above tests (i) to (xv). The results are shown in Table 3.

Examples 16 to 28, Reference Examples 1 to 7

Except that the mixing composition of the coating for forming the touch-surface-side hardened coating was changed to any of Tables 3 to 6, the same procedures as in Example 15 were performed, and the production of an adhesive film, physical measurement, and evaluation were performed. The results are shown in any of Tables 3 to 6.

Example 29

Except that the blending composition of the coating for forming the touch-surface-side hardened coating was changed to Table 6, the rest were the same as in Example 1, and production of an adhesive film, physical measurement and evaluation were performed. The results are shown in any of Tables 3 to 6.

Example 30

The tip discharge treatment was performed on both sides of the above (α-14) with a processing capacity of 167W · min / m ² (discharge power is 500W, the length of the discharge electrode is 1m, and the production line speed is 3m / min). The wetness index on both sides is 63mN / m. Next, on one side, a coating device using a mold method and a coating composition with the composition shown in Table 6 were used as the coating for forming the hardened coating on the touch surface side, and the coating was applied so that the thickness after hardening was 15 μm; On one side, the coating was applied using a mold-type coating device and the above-mentioned (ε-1) was used as the coating surface-side hardened coating-forming coating so that the thickness after hardening was 15 μm to obtain a hardened coating laminated film. Next, on the hardened coating layer on the printing surface side, the above-mentioned (γ-1) was coated with a glue to make the thickness after hardening to be 30 μm, and heated and hardened at 130 ° C. for 1 minute to obtain an adhesive film. The obtained adhesive films were subjected to the above tests (i) to (xv). The results are shown in Table 6.

Comparative Example 1

On one of the surfaces (α'-1), a coating device using a mold method and a coating composition with the composition shown in Table 6 were used as a coating for forming a hard coating on the touch surface side, and the coating was applied so that the thickness after hardening was applied. 15 μm; on the other side, a coating device using a mold method was used to apply the coating material for the above-mentioned (ε-1) as a hardened coating on the printing surface side so that the thickness after hardening was 15 μm and hardened. Coated laminate. Next, on the hardened coating layer on the printing surface side, the above-mentioned (γ-1) was coated with a glue to make the thickness after hardening to be 30 μm, and heated and hardened at 130 ° C. for 1 minute to obtain an adhesive film. The obtained adhesive films were subjected to the above tests (i) to (xv). The results are shown in Table 6. In addition, the linear expansion coefficient increases the shrinkage of the test piece, and the measured value cannot be obtained.

Comparative Example 2

Except that the above-mentioned (α'-2) was used in place of the above-mentioned (α'-1), the same procedure as in Comparative Example 1 was performed, and an adhesive film was produced, and physical properties were measured and evaluated. The results are shown in Table 6.

Comparative Example 3

Except that the above-mentioned (α'-3) was used in place of the above-mentioned (α'-1), the same procedures as in Comparative Example 1 were performed, and an adhesive film was produced, and physical properties were measured and evaluated. The results are shown in Table 6.

As can be seen from the results shown in Tables 3 to 6, the adhesive film provided with the hardened coating layer of the present invention is a characteristic that can be preferably used as a protective film for a display panel. On the other hand, Comparative Example 1 (without a poly (meth) acrylimide resin film layer) had poor heat-resistant dimensional stability (coefficient of linear expansion) and a hard surface. Degree is not good. Comparative Example 2 (without a poly (meth) acrylimide resin film layer) had poor heat resistance dimensional stability. Comparative Example 3 (containing no poly (meth) acrylimide resin film layer) had poor heat resistance dimensional stability and surface hardness.

Claims (8)

An adhesive film includes (δ) a hardened coating layer, (α) a poly (meth) acrylimide resin film layer, and (γ) an adhesive layer in this order from the surface layer side, wherein (δ) is hardened The coating layer is composed of: (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.2 to 4 parts by mass of a compound having alkoxysilyl and (meth) acryloyl ; (C) 0.05 to 3 parts by mass of organic titanium; and (D) active energy ray-curable resin composition composed of 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm, and a total light transmittance of 80% . The adhesive film according to item 1 of the patent application range, wherein the active energy ray-curable resin composition further contains (E) water repellents at 0.01 to 7 parts by mass. The adhesive film according to item 2 of the scope of the patent application, wherein the (E) water-repellent agent comprises a (meth) acryloyl-containing fluoropolyether water-repellent agent. The adhesive film according to item 1 of the scope of the patent application, wherein the (α) poly (meth) acrylimide resin film layer satisfies the following characteristics (I) and (II) (I) The total light transmittance is 85 % Or more; (II) The haze value is 3.0% or less. The adhesive film according to item 1 of the scope of patent application, wherein the (α) poly (meth) acrylimide resin film layer is directly and sequentially laminated: the first poly (meth) acrylimide resin layer (α 1); an aromatic polycarbonate resin layer (β); and a second poly (meth) acrylimide resin layer (α 2). The adhesive film according to any one of claims 1 to 5, wherein the (γ) adhesive layer contains a silicon adhesive. An adhesive film for use as a component of an image display device according to any one of claims 1 to 6. An image display device component includes the adhesive film according to any one of claims 1 to 5.